TW201034969A - Method for manufacturing a powder for the production of p-type transparent conductive films - Google Patents

Abstract

This invention relates to material compositions, a manufacturing method for these materials and a manufacturing method for ceramic bodies, to be used as targets in physical vapour deposition techniques of p-type transparent conductive films. There is disclosed a method for manufacturing a pelletized oxide material MxSr1-xCu2+aO2+b, wherein -0.2 ≤ a ≤ 0.2, -0.2 ≤ b ≤ 0.2, and M is either one or more of the group of bivalent elements consisting of Ba, Ra, Mg, Be, Mn, Zn, Pb, Fe, Cu, Co, Ni, Sn, Pd, Cd, Hg, Ca, Ti, V, Cr; with 0 ≤ x ≤ 0.2; comprising the steps of: providing a precursor mixture having a given grain size distribution, and comprising stoichiometric quantities of Cu2O, Sr(OH)2.8H2O, and, when 0 < x ≤ 0.2, M-hydroxide, intimately mixing said precursor mixture so as to obtain a homogeneous mixture, and sintering said homogeneous mixture at a temperature above 850 DEG C. The oxide material SrCu2+aO2+b has a residual carbon content of less than 400 ppm, and a target having a density of at least 5.30 g/ml can be manufactured with it.

Description

201034969 VI. Description of the Invention: [Technical Field] The present invention relates to a material composition, a method for producing the same, and a method for producing a target in a physical vapor deposition technique of a P-type transparent conductive film. [Prior Art] In recent decades, the development of transparent conductive oxides has been in progress. IΤ(Indium Tin Oxide) has the lowest resistance-preserved transparent conductive oxide obtained so far, and combines ~1 (the resistivity of Γ4 Qcm sees the light-NIR spectral range up to 80-90% transparency. E-aluminum Zinc oxide (Ζ η O : A1 ), and it is a substitute for many applications, but its performance is still slightly inferior to the performance of I Τ 电阻 (resistance translation > 1 (T4 Qcm). However, 'show this magnitude All of the transparent conductive materials are all n-type conductive oxides. Therefore, although they have excellent characteristics, their applications only require the application of transparent conductive electrodes, such as illuminating devices, flat volts devices, smart windows, etc. In order to create a novel type of electro-optic device, a p-type transparent conductive oxygen quality P-type transparent conductive oxide is also required to be obtained by allowing the transparent surface of the material and the existing n-synthesis transparent active device. This enables the formation of UV light to be combined with phosphors, transparent electronic circuits, sensors, etc. to form the type of display. In the past, many researchers and inventors have been waiting for the length of the porcelain. η 和 在 在 在 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物 氧化物However, the resistivity of the P-type transparent conductive oxide that has been identified so far is at least one order of magnitude higher than that of the n-type counterpart, and usually requires a high temperature for forming a thin film. For an example, refer to P·Kawazoe et al. Ypee 1 ectrica 1 conduction in transparent thin films of CuA102, Nature, 3 89, 939-942 (1 9 9 7 ); and H. M izo gu chi et al.

Phys. Lett., 80, 1 207- 1209 ( 2 0 0 2 ), H. 0 h t a, etc.

Solid-State Electronics, 47, 226 1 - 2267 (2003) &gt; These two documents explore AM〇2 construction materials in which a is a cation and M is a positive ion such as CuA102. Although the performance of such p-type transparent conductive oxides known to date is still poor, a number of studies have been proposed for forming transparent pn junctions, such as K. Tonooka et al., Thin Solid Filins, 445, 3 27 , (2003) proposed a transparent diode based on pn homojunction (CuIn〇2); and H. Hosono et al., Vacuum, 66, 419 (2 002), using p_n heterojunction Photoelectric device (p_

SrCu2〇2/n-ZnO). Other materials are p-ZnRh204/n-Zn0 UV-LED, p-NiO/n-ZnO UV detector, UV-detection based on p-η heterojunction diode composed of transparent oxide semiconductor Detectors, such as p-Ni〇/n-ZnO' and P-CuA102/n-Zn0 photovoltaic cells and transparent electronic components. However, because the material quality is not good, the non-optimal resistivity and the carrier concentration of the P-type transparent conductive oxide or the interface of the heterojunction are not clear, the performance of the diodes is not good, thus making the ideality factor ) not less than 1 · 5, V &lt; 4V forward current versus reverse current ratio between 1 0 -6- 201034969 and 80 'breakdown voltage less than 8 volts' series resistance increased, and turn-on voltage Does not necessarily correspond to the energy band gap of the materials. The transparency of these devices is between 40% and 80%.

The results of the research by Kawazoe and Hosono's group (eg, Yan. et al., J. Electroceram., 4, 407 (2000)) have formed many p-type transparents containing oxides of Cu(I). Description of conductive oxides. The pn consisting of p-SrCu2〇2 and n-ZnO is successfully fabricated by heteroepitaxial thin film growth (as proposed in H. Ohta et al., Electron. Lett., 36, 984 (2000)). A heterojunction-based emitting UV diode. Among these p-TCO materials, SrCu2〇2 (also known as SCO) is the most promising material for electronic devices, mainly because the epitaxial film can be obtained at relatively low temperatures to avoid junction regions. The interface reaction. Although the synthesis of an undoped and K-doped SrCu202 film has been proposed (for example, as proposed in US 6,294,274 B1), the effect of the dopant on the photoelectron properties of SrCu202 is not fully understood, and is currently a Q-stop SrCu202 film. The conductivity is still less than the conductivity of other p-type TCOs. Many of the reports mentioned above relate to depositing films from solution. Other common techniques for depositing thin films are covered by the general term for physical vapor deposition, including but not limited to diode and magnetron sputtering, reactive sputtering, vacuum evaporation, pulsed laser deposition (PLD), and thunder. Laser ablation, IAD, etc. These technologies mainly use solid ceramics or metals, so-called targets. It is known in the art that ceramic bodies or targets used in such techniques preferably have high density (low porosity) and uniformity 'and preferably do not have multiple compounds and phases to avoid during deposition or manufacturing. Shape 201034969 The film produced preferential preferential plating and concentration and composition non-uniformity.

Sheng et al., &quot;Oriented growth of p-type transparent conducting Ca-doped S r C u 2 0 2 thin films by pulsed laser deposition&quot;, Semicond. Sci. Technol., 21, 5 8 6-5 90 ( 2006 ) Pulsed laser deposition on a doped SCO film is proposed. The PLD target was prepared from a polycrystalline doped Ca SrCu202 powder which was synthesized by heating a mixture of Cu20, SrC03 and CaC03. First, a pure powder of Cu20 (99.9%), SrC03 (99.9%) and CaC03 (99.99%) having an atomic ratio of 10:9:1 was taken and thoroughly mixed in a ball mill for 24 hours. Then, the mixture was heated at 900 ° C for 15 hours in an argon atmosphere. The sintered body was further honed and pressed into a small nine, and the small 90-hour was sintered at 900 ° C in an argon atmosphere, which was used as a P LD target. This method outlines the latest technology for manufacturing P LD targets. In U S 7 0 8 7 5 2 6 B 1 , a method of producing a p-type doped Ca ◦ SrCu 2 〇 2 film by spin coating an acetate precursor mixture is disclosed. The manufacture of transparent conductive films using physical vapor deposition techniques to date has revealed many technical problems associated with the properties of the ceramic body materials used. The materials available today are not dense enough and are not uniform. These problems are associated with the use of excessive temperatures in the formation of the target and the presence of residual carbon contamination in the target. These issues will be exemplified in the comparative examples below. [Summary of the Invention]

SUMMARY OF THE INVENTION An object of the present invention is to provide an improved method for producing a transparent conductive oxide of P-8-201034969 type containing bismuth, copper and oxygen, and a target for physical vapor deposition which does not have the aforementioned problems. According to the present invention, a niobium oxide material MxSri.xCvi2 + a〇2+b (where _〇.2$aS〇.2, -0.2sbf0.2, and Μ is made of Ba, Ra 'Mg, Be One or more of a group of divalent elements composed of Mn, Zn, Pb, Fe, Cu, Co., Ni, Sn, Pd, Cd, Hg, Ca, Ti, V, Cr; The process of x SO · 2 ) comprises the steps of: - providing a precursor mixture having a given particle size distribution, and comprising a stoichiometric amount of Cu20, Sr(OH) 2.8 Η 20, and when 0 &lt; XS 0.2 Μ-Hydroxide, - intimately mixing the precursor mixture to produce a homogeneous mixture, and • sintering the homogeneous mixture at a temperature above 850 °C. Preferably, during the step of intimately mixing the precursor mixture, the particle size distribution is retained, and between the step of intimately mixing the precursor mixture and sintering the homogeneous mixture, the homogeneous mixture preferably undergoes 6 (TC Q) The calcination step at a temperature between 1 〇〇 ° C. The intimate mixing step is preferably carried out in a Turbula mixer, and the calcination step is preferably carried out in a vacuum drying step. In a specific example, The method additionally comprises subjecting the niobium oxide material to a hot compaction cycle at a temperature above 950 ° C and at a pressure of at least 2.5 kN/cm 2 , preferably at least 3.5 kN/cm 2 . The solid cycle is preferably carried out at a temperature between 975 and 1 〇 25 t. In a preferred embodiment, x = l ± 〇.2, M^ = Ba, and the M-hydroxide system B a ( Ο Η ) 2 · 8 Η 2 Ο -9- 201034969 The invention also includes a powdered oxide material SrCU2+a〇2+b, wherein -0.29S0.2 ' -0.251^0.2 ' residual carbon content is less than 400 Ppm. The powdered oxide material is used to make a target, wherein the density of the fertilizer is 5% less than 30 g/ml, and may be obtained by a process comprising the steps of: - sintering the homogeneous mixture at a temperature above 850 ° C, thereby producing a niobium oxide material, and - subjecting the pelletized oxide material to a hot compaction cycle at a temperature above 95 ° C and at a pressure of at least 2.5 kN/cm 2 , preferably at least 3.5 kN/cm 2 . The density of the target is at least 5.40, or even 5.45 g/ml. In a preferred embodiment, the target is for PVD deposition of a p-type transparent conductive film, such as magnetron sputtering. The present invention will show The temperature and time of the process are lower and lower than those of the prior art, and it is unexpectedly observed that the powder purity of the powder produced by using the improved method and the uniformity of the ceramic body obtained from the powder are significantly improved. The invention is further illustrated by the following (reverse) examples. Counter Example 1: Latest Technology Product (CE1) A bismuth oxide (SCO) film manufactured by pulsed laser deposition (PLD) is available from STMC (Westerville, OH, USA). It

Sputtering Target Manufacturing Company). The targets were analyzed using the A-10-201034969 Kimide principle to show a density of (3.90 ± 0.10) g/ml (s.d.; n = 3). The SEM picture of the cross section of the just ruptured surface (shown in the left half of Figure 1 (CE1)) can be seen to have a high degree of porosity which results in a relatively low target density. The X-ray diffraction pattern is studied (as shown in the lower half of Fig. 2 (C E1 )). The measurable target is mainly composed of beryllium copper oxide and copper oxide CuO [01-080-1268], and contains trace amounts. Carbon and only trace target compound Cu2Sr02 [〇〇-〇38-1178]. (The number between the square brackets refers to the collection number of the Diffraction Data® of the JCPDS-International Centre.) The X-ray composition of the line scan and the masking mode constitutes a microanalysis (energy dispersive spectrometer) ) Further analysis was performed on the polished cross section. This analysis confirms (see Figure 3 (CE1) to become clearer) the porosity of the target sample and the rather non-uniform nature of the material. Many of the target methods described in the test literature are due to the overall difficulty of finding the right target on the market. Counterexample 2: The method described in the literature a) Suzuki-Gauckler method - in Suzuki, Ryosuke 0; Bohac, Petr; Gauckler, Ludwig J. Thermodynamics and phase equilibria in the strontium-copper-oxygen system, Journal of the American Ceramic Society (1 992 ), 7 5 (1 0), 2 8 3 3 -42, a typical ceramic method for making multi-metal oxides (mixing - -11- 201034969 shaking and baking) . The starting materials for this process were CuO and SrC03 (380.0 g and 357.0 g, respectively), which were sieved through a 200 mesh screen. The starting material therefore consists of a mixture of powders of less than 75 μm and is further homogenized by Turbuta mixing. The following process was then carried out: Step 1: Calcination in air at 950 °C for 200 hours Step 2: Milling the calcined powder in a ring mill until all the powder passed through a 200 mesh screen (&lt;75 μηι Step 3: Cold compaction of the powder into small nine Step 4: Sintering at 900t in argon for nine nine hours 6 Step 5: Milling the sintered small nine in a ring mill until all the powder passes through the 200 mesh screen Net (&lt;75 μιη) (analysis) Step 6: Cold compaction of the powder into small nine Step 7: Sintering at 900 °C in argon for nine to eight hours Step 8: Milling in a ring mill Sintered small until all the powder passed through a 200 mesh screen (&lt;75 μηι) (analysis). Step 9: Cold compaction of the powder into small nine steps 1 〇: Sintering at 90 (TC) for 9:17 hours in argon Step 1 1 : Mill the sintered pellets in a ring mill until all the powder passes through a 200 mesh self-twisting net (&lt;75 μηι) (analysis). Step 1 2: Cold compaction of the powder into small nine steps 13: in argon Sintering at 900 ° C for 9 to 66 hours in the gas. Step 1 4: Sintering at 7 7 5 ° C in nitrogen (1 〇〇 1 /h) for 9 to 12 hours - 201034969 Nine shows a density from 4.59 to 5.00 g/ml (Archimedes method). After the first calcination (step 1), after step 1 1 and at the end of the procedure (step 14), the powder sample is X. Ray diffraction analysis. Figure 4 (lower line: after the step 1 'the line in the middle: after step 1 1 , the line above: at the end of the program) shows the substantial changes that occurred during the procedure of the method. The peak of each sample is normalized to the highest peak and is randomly displaced on the y axis. But even after the total program time is more than 300 hours (or nearly two weeks), it is clear that this method will not produce The desired product. The final diffraction pattern represents the majority of the SrCu〇2 phase, which is contributed from the target compound SrCu202. The lesser part is also derived from Cu20, CuO and Sr14Cu2404i. b) Modified Margins ο η - G i η 1 ey Method This method uses a direct deposition of a film from an aqueous precursor, see A Martinson's Synthesis of single phase S rCu2 02 from liquid precursors, DOE Energy Research Undergraduate Laboratory Fellowship Report, Nationa l Renewable energy Laboratory, Golden, Co (2002). Since this method has been developed for the direct deposition of a film of a coffin compound, it has been modified to obtain a powder for further processing and conversion into a solid body which can be used as a target for physical vapor deposition. The original process started with a solution of copper formate (Cu (CH200) 2.4H20) and strontium acetate (Sr(CH3COO) 2) with a Cu:Sr ratio of exactly 2:1. This solution was applied to the substrate by a spray technique. The substrate was heated from -13 to 201034969 to 180 °C. The substrate having the deposited film was then annealed at 775 t in a 2.0 Torr. 5 Torr atmosphere for 4 hours. At the end of the annealing period, the substrate was cooled to room temperature (the oxygen flow was stopped at 65 °C). In this modified method, the raw material used to make the powder is the same as the Martinson-Ginley method, but the process is modified as follows: • Spray drying the solution at 180 ° C • Annealing at 775 ° C in nitrogen 4 Hour • After cooling to room temperature under nitrogen, 1140.0 g and 500.1 g of copper formate (tetrahydrate) (Aldrich, 97%) and cesium acetate (Aldrich) were dissolved in 3_92 1 of demineralized water, respectively. The solution was spray dried in a Niro laboratory scale spray dryer (S80) equipped with an atomizer (SL 24_5 〇 / M - 〇 2 / B, with straight channels [493 - 1 8 8 9_019]). The spray dried powder was heated to 775 ° C in a tube furnace and maintained at 775 ° C for 4 hours under a nitrogen atmosphere. The precursor powder was loaded with about 3/4 of the quartz crucible. Significant volume expansion was observed during the simmering. It is clear from the XRD pattern in Fig. 5 that the XRD spectrum and the expected powder pattern intensity (below) with pure SrCu202 (top), Ca-substituted SrCu202 (middle) (taken from JCPDS 3 8 - 1 1 78 -

Figure 6 of the International Centre's Diffraction Data®) is a mixture of products that are not pure phase after calcination.

The spray drying and calcination of the resulting powder can often be replaced by direct spray combustion or spray pyrolysis techniques from the point of view of the manufacture of the sequence of the homogeneous solution. This method starts with the same precursor described above but uses spray combustion at 580 ° C -14 - 201034969 instead of the spray drying step at 180 °C. The resulting powder was further annealed as described in step b) at 77 5 °C. The main phases formed by these conditions were the rhombohedrite (SrC03), the black copper ore (CuO), the copper (I) oxide (Cu20) and copper. An unknown copper loss was also observed. This method cannot be continually determined to produce the correct composition. It shows that in the material starting from the carbon-containing rhombohedrite, the rhombohedral ore is the final product _. The lanthanum carbonate is a very stable compound having a decomposition temperature of 1 075 °C.较低 A lower decomposition temperature of about 800 ° C can be observed in an oxidizing atmosphere, however the report indicates that the decomposition is about 1220 ° C in the CO 2 atmosphere. Since the production of the target compound requires a non-oxidizing environment (to avoid the oxidation of Cu(I) to the Cu(II) state), the decomposition temperature of any carbonate formed will be higher than 1 0 50 t:. c) K u d 〇 method

From the observations of previous methods, the stability of strontium carbonate can be evaluated by the method inspired by Kudo's research: see Kudo, A.; Yanagi, H·; Η os ο η ο, Η.; Kawazoe, Η. A new p-type conductive oxide with wide band gap, S r C u 2 O 2 , Materials Research Society Symposium Proceedings (1 9 9 8 ) , 526 ( Advances in

Laser Ab 1 at i ο η o f M at er i a 1 s ) , 2 9 9 - 3 04, and Kudo,

Atisushi; Yanagi, Hiroshi; Ueda, Kazushige; Hosono, Hideo; Kawazoe, Hiroshi; Y ano, Yo shihiko's Fabrication of transparent pn heterojunction thin-film diodes based -15- 201034969 entirely on oxide semiconductors, Applied Physics Letters (1 999 ), 75 (18), 2851 - 2 853. As a starting material, the process uses c u 2 O and s r C O 3 , which are mixed in a stoichiometric ratio of 2:1 Cu:Sr. The raw materials were intimately mixed and milled in a Retsch ZM100 mill equipped with a 120 μηι net. The mixture was placed in a stream of nitrogen (24 Torr / h) at 950 ° C for 40 hours. After cooling the sintered body under nitrogen, the product was further honed and pressed into a small nine by a cold pressure of 800 kg/cm2. The pellet obtained was sintered in nitrogen at 850 ° C for 1 hr. Chemical analysis of the powder showed (in terms of mass percentage) that the obtained product contained (35.23 ± 0.07) mass% of Sr and (51.19 ± 0.06) mass% of Cu. Residual carbon pollution amounts to 〇 · 〇 4 3 - 〇 . 〇 5 9 mass% of C. X-ray powder diffraction knows that in this method, we obtain the correct material phase with a small amount of metallic copper impurities. As shown in Fig. 7, the powder diffraction pattern of the calcined powder is provided, and its peak position table (below, upper line) And the peak position table of SrCu202 [00-03 8 -U78] (lower figure, middle line) and (:11[01_070-3 0 3 9 ] (lower figure, lower line). The powder is cold compacted. Sintering with lower pressure, but the result becomes very brittle 'there is no major improvement in density. The resulting small IX breaks during polishing. Therefore 'change the compaction method to hot pressing. The following thermal cycle is used to compact the method Powder obtained (30 mm graphite mold, coated with boron nitride) 1 · Cold compaction at 20 kN 2. 50 ° at minimum load (4 kN) (: / min heating

3_ at 900 ° C download weight increased from 4 to 10kN -16- 201034969

4. Increase the download weight from 10 to 20kN at 975 °C 5. Pause for 30 minutes at 975 °C 6. The density of the target obtained by natural convection cooling is 5 · 3 3 ± 0 . 1 0 g/m 1 . Example 3: Example of "carbonate-lean method" according to the present invention 0 Although it is considered from the above that carbonate is used as a starting material

The final product of the Kudo process has a lower carbon contamination and the temperature used is on the low temperature side of the complete thermal decomposition, but attempts have been made to further reduce the amount of carbon in the material as a substrate impurity. Therefore, a method similar to the Kudo method but using Sr(OH) 2_8H2 oxime as a reactant was developed. This method is called "carbonate-lean method". In the industry (for example, S ο 1 v a y S A ), the most common form of Sr ( OH ) zHO is a Sr-hydroxide. A batch of Kudo and the lean carbonate method were simultaneously performed to prepare and analyze the ruthenium sample under the same conditions. The X-ray diffraction pattern in Fig. 8 summarizes the two methods (Kudo method: upper 'carbonation-lean method: lower). It has been identified that both materials are SrChO2', and it is apparent that some trace impurities (such as copper in the Kudo case) are present.

The carbon content of the final product of the Kudo method and the lean carbonate method was 0.072% and 0.03 4%, respectively. The carbon contamination present in the products of the present invention may mean that the barium hydroxide raw material absorbs carbon dioxide from the atmosphere rather than from the carbonate used. Sufficient materials are fabricated to explore the conditions that result in a higher density compaction procedure that is advantageous in the development of the target as -17-201034969. The compaction procedure of Method 2-c is used in a modified manner where the control parameters such as temperature, pressure, and duration are varied to produce the results of the table below. Table 1: Compaction Results Temperature rc) Pressure (kN) Time (min) P (g/ml) 975 20 30 5.439 975 20 45 5.345 975 25 30 5.411 1025 20 30 5.414 1025 25 30 5.472 1025 20 45 5.425 975 25 45 5.446 1025 25 45 5.458 (P: Density) It should be noted that the pressure is expressed as a force applied to a target of 3 cm diameter (surface: 7.07 cm2), 20 kN is equivalent to 2.8 3 kN/cm2, and 2 5 kN is equivalent. 3.54 kN/cm2. The conclusion is that higher densities can be achieved using increased pressure and temperature that have a positive effect on density and a longer duration with a few negative effects. However, care should be taken not to excessively increase the temperature and extend the duration to avoid decomposition. Compared to the target of the counterexample 1, the target of the method of the present invention exhibits a far more pure phase, and the target compound and only a small amount of other impurities associated with the starting product are indeed present. This is shown in Figure 2: upper part: material of the invention (carbonate-depleted), lower part: material of the reverse example 1. -18- 201034969 On the SEM image of the cross-section of the just-ruptured surface, as shown in Figure 1 - right half (Example 3), it can be seen that the material has much fewer pores than the material of Example 1. See Figure 3 (Example 3 vs. CE1), comparing the analysis of elemental oxygen (upper right), copper (lower left) and 缌 (bottom right) by X-ray composition microanalysis (energy dispersive spectrometer), noting the invention The composition has a higher uniformity of composition. Therefore, the composition change (Sr/Cu ratio) in the sputter film is small at the expected ablation/intrusion uranium depth (assuming there is no preferential ablation/invasion or sputtering). ❸ Since the raw material can be observed during the milling step in Retsch ZM100, 'the use of Sr ( OH ) 2·8Η20, the release of crystal water makes the powder mixture into a viscous paste, preferably in a Turbula mixer. Mechanical mixing was carried out for 1 hour instead of the Retsch ZM100 centrifugal separation milling step 'and then dried under vacuum at 8 CTC. It should be noted that both materials show the same and desired X-ray diffraction pattern (see Figure 9: top: using a Retsch mill; bottom: using a Turbula mixer), which is more pronounced in the powder Q obtained using the original process. A trace of Cu20. Despite the use

The inherent mechanical problems caused by the Sr ( OH ) 2.8H20 milling method, but can be summarized as the same material and suitable for the manufacture of targets. The untreated powder obtained was tested under heat treatment conditions. The formation of the paste was avoided using a suitable mixing and vacuum drying step and was observed twice in a Retsch ZM100 mill (and sieved at 80 μπι) after a 40 hour hot pressing step at 950 ° C in nitrogen. The quality of the mill was reduced by 19.6%, compared to 33.3% of the original process (using the "original" Retsch centrifugal milling step). The pressing cycle forms a color change from black to gray -19- 201034969. For "raw process" powders, a color change indicates oxidation or modification has occurred. From the analysis of the remaining material, it is known that a small amount of initial product (i.e., barium hydroxide) can be found in the calcined material, and it is likely to induce other unintended reactions during the hot press cycle. If the vacuum drying step is omitted before the hot pressing cycle after the Turbula mixing, the result becomes that all the targets are broken into powder after compaction and cooling. This is not the case with targets formed using the Retsch or Turbula and vacuum dried carbonate lean processes. Even if the cost of forming a paste in the mill is an additional mixing/drying step, the preferred method for upgrading the manufacturing should avoid this. Example 4: Preparation of target BaSrCu202 Similar to Example 3, the target manufacturing method can be summarized as follows: Weighing Cu20, Sr(OH) 2.8H20 and Ba(OH) 2.8H20=&gt; Mixing components using a Turbula mixer =&gt; Under vacuum at 80-9 (TC dry component for 4 days => mixed in a Retsch ZM100 centrifugal mill and milled to 80 μηι =&gt; in a furnace under nitrogen at 950 °C The reaction was carried out for 40 hours = &gt; mixed in a Retsch ZM100 centrifugal mill and milled to 250 μm =&gt; mixed in a Retsch ΖΜ1 00 centrifugal mill and milled to 80 μm =&gt; Packaging & Sealing =&gt; Compaction, cold pressing => Heating to 9 7 5 °C and maintaining the temperature => Cooling => -20- 201034969 Honing and polishing. [Simple description] The following diagram illustrates this text. Invention: Figure 1: Comparison of SE Μ images of a cross section of a target material. Figure 2: Comparison of X-ray diffraction patterns of prior art and products of the present invention. Figures 3 a and 3 b: prior art and products of the present invention EDS line analysis and face composition analysis Figure 4: XRD evolution during the entire synthesis of the Suzuki-Gauckler method Figure 5: Powder diffraction of calcined powder by Martinson-Ginley method

Figure 6: XRD 0 /2 0 spectrum and expected powder pattern intensity of the overall phase SrCu202, Ca-substituted SrCu202 Figure 7: Powder diffraction pattern of the calcined powder of Kudo method, its peak list and SrCu202 and Cu Peak position chart Figure 8: Comparison of Kudo and X-ray diffraction patterns of the Carbonate lean method Figure 9: Comparison of X-ray diffraction patterns of different carbonate-poor methods-21 -

Claims (1)

201034969 VII. Scope of application for patents: 1. A method for manufacturing MxSri xCU2+a〇2+b, which is made of niobium oxide material, of which -0.29S0.2' -0.24S0.2, and M is made of Ba, Ra One or more of a group of divalent elements composed of Mg, Be, Mn, Zn, Pb, Fe, Cu, c〇, Ni, Sn, Pd, Cd, Hg, Ca, Ti, V'Cr Wherein O^xSO·2; the method comprises the steps of: - providing a precursor mixture having a given particle size distribution, and comprising a stoichiometric amount of Cu20, Sr(OH) 2.8H20, and when 0 &lt; A cerium-hydroxide is included, - the precursor mixture is intimately mixed to produce a homogeneous mixture, and - the homogeneous mixture is sintered at a temperature above 850 °C. 2. The method of claim 1, wherein the step of intimately mixing the precursor mixture maintains the given particle size distribution, and between the step of intimately mixing the precursor mixture with sintering the homogeneous mixture, The homogeneous mixture is subjected to a calcination step at a temperature between 60 ° C and 100 ° C. 3. The method of claim 2, wherein the intimate mixing step is carried out in a Turbula mixer. 4. The method of claim 2, wherein the calcining step is a vacuum drying step. 5. The method of any one of claims 1 to 4, which additionally comprises, by a temperature above 950 ° C and at least 2.5 kN/cm 2 , preferably at least 3.5 kN/cm 2 The step of preparing the target by subjecting the niobium oxide material to a hot compaction cycle under pressure. -22- 201034969 6. The method of claim 5, wherein the hot compaction cycle is carried out at a temperature between 975 ° C and 10 ° ° ° C. 7. The method of any one of claims 1 to 6, wherein 〇&lt;x£〇.2' M = Ba and the M-gas oxide is Ba(OH) 2.8H2O. 8. A powdered oxide material SrCu2 + a02 + b, wherein -0.2950.2, -〇.2SbS〇.2' has a characteristic residual carbon content of less than 4〇〇ppm, and may be as claimed in the patent application The method of any one of items 1 to 7 is prepared. 9. A use of a powdered oxide material as claimed in claim 8 for the manufacture of a target having a density of at least 5.30 g/mi and which may be obtained by a process comprising the steps of: - above Sintering a homogeneous mixture as in claim 1 of the patent at the temperature of 850 ° C, thereby producing a niobium oxide material, and - at a temperature above 95 ° C and at least 2.5 kN / cm 2 , Preferably, the niobium oxide material is subjected to a hot compaction cycle at a pressure of at least 3 · 5 kN/cm 2 . 10. The use of claim 9, wherein the target has a density of at least 5.40 g/ml', preferably 5 45 g/ml. 1 1. The use of the ninth or tenth aspect of the patent application for the preparation of a target for pVD deposition of a P-type transparent conductive film. -twenty three-